CN114345319B - Modified nano cerium oxide catalyst, preparation method thereof and application thereof in dimethyl carbonate synthesis - Google Patents
Modified nano cerium oxide catalyst, preparation method thereof and application thereof in dimethyl carbonate synthesis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 30
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims description 14
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012024 dehydrating agents Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002250 absorbent Substances 0.000 claims 2
- IBBMAWULFFBRKK-UHFFFAOYSA-N picolinamide Chemical compound NC(=O)C1=CC=CC=N1 IBBMAWULFFBRKK-UHFFFAOYSA-N 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 14
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a modified nano cerium oxide catalyst and a preparation method thereof, and application of the catalyst in direct synthesis of dimethyl carbonate from carbon dioxide and methanol. The method is a freeze drying method in the process of preparing the nano cerium oxide catalyst by a hydrothermal method, and can effectively improve the catalytic activity of the nano cerium oxide catalyst on the methyl esterification reaction of carbon dioxide. The preparation method of the modified nano cerium dioxide can obtain a high-activity catalyst, and when the catalyst is used for the reaction of synthesizing dimethyl carbonate from carbon dioxide and methanol, a dimethyl carbonate product can be obtained with high yield, and the selectivity of the dimethyl carbonate is close to 100%.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a modified nano cerium oxide catalyst and a preparation method and application thereof, and particularly relates to application of the catalyst in direct synthesis of dimethyl carbonate from carbon dioxide and methanol.
Background
Dimethyl carbonate (DMC) is considered an environmentally friendly green chemical, and because it contains methoxy and carbonyl groups in its molecule, it can replace the highly toxic dimethyl sulfate and monohalomethane as methylating agents, and phosgene as carbonylating agents. In addition, DMC is often used as an additive to gasoline and octane booster in place of the environmentally harmful methyl tertiary butyl ether due to its high oxygen content. The traditional synthetic methods of DMC generally have three types: phosgene processes, methanol oxidative carbonylation processes and transesterification processes. The direct synthesis of DMC by CO 2 and methanol can effectively solve the problem of easy corrosion caused by extremely toxic substances in the traditional method. However, the high activation energy barrier of CO 2 and the thermodynamic limitations of the reaction make it critical to find a suitable catalyst for the reaction.
In recent years, as the green chemistry concept goes deep, the search for efficient catalysts for synthesizing DMC from CO 2 and methanol has attracted extensive attention, and nano-ceria and metal doped cerium-based catalysts are the hot spots of current research. Patent document with publication number CN104841414A discloses a nano cerium oxide catalyst, wherein factors of temperature disturbance are introduced in the preparation process of a common hydrothermal method, the catalytic activity of the catalyst is changed by changing the number of temperature disturbance, and the DMC yield reaches 16.78mmol g -1 cat. Patent publication CN112823879a discloses a metal doped cerium based catalyst with high specific surface area, low pressure drop and excellent stability, with a methanol conversion of 24.3% and a selectivity of 78.6% for dimethyl carbonate at 140 ℃. The publication No. CN110479236A discloses a catalyst of various oxide compounds, which is prepared by one to three of CeO 2、La2O3 and ZrO 2 according to different mass ratios, and has DMC yield of 4.13mmol g -1 cat and selectivity of 100%. However, the catalytic performance of these catalysts is far from reaching the level of industrial application.
Therefore, on the basis of the prior art, the CeO 2 catalyst with high efficiency, high selectivity and high stability is prepared by improving the preparation method of the catalyst, and is a key step for realizing the industrialization of directly synthesizing DMC (direct synthesis of CO 2 and methanol).
Disclosure of Invention
The invention provides a modified nano cerium oxide catalyst, a preparation method and application thereof in synthesizing dimethyl carbonate, and the modified nano cerium oxide catalyst has better catalytic performance when being applied to synthesizing the dimethyl carbonate, and can effectively improve the conversion rate of reactant methanol.
In order to solve the technical problems, the technical scheme of the invention is as follows:
The preparation process of modified nanometer cerium oxide catalyst includes the following steps:
(1) Dropwise adding a cerium nitrate solution into a sodium hydroxide solution, and obtaining cerium hydroxide suspension under the stirring condition;
(2) Adding the cerium hydroxide suspension obtained in the step (1) into a reaction kettle for aging, then washing the cerium hydroxide with alcohol and water, dispersing the obtained cerium hydroxide in deionized water, carrying out ultrasonic vibration, freezing overnight, and then carrying out freeze drying;
(3) Calcining the dried cerium hydroxide powder to obtain the nano cerium oxide catalyst.
The method adopts a freeze drying method in the process of preparing nano cerium dioxide by a hydrothermal method, so that the specific surface area, the porosity and the oxygen cavity content of the catalyst are improved, and the activity of the catalyst is improved.
And (3) 30-50 mL of deionized water for dissolving 8-10 g of sodium hydroxide and 5-10 mL of deionized water for dissolving 0.8-1 g of cerium nitrate.
Preferably, in the step (1), the stirring speed is 400-800 rpm, and the stirring time is 20-40 min;
In the step (2), the aging time is 10-14 h, the times of alcohol washing and water washing are 3-5 times, and the ultrasonic time is 20-40 min.
Preferably, in the step (2), the freeze-drying temperature is-60 to 80 ℃ and the freeze-drying time is 10 to 14 hours.
Preferably, in the step (3), the calcination temperature is 600-800 ℃, the calcination time is 4-6 h, and the temperature rising rate is 2-5 ℃/min.
The invention also provides a modified nano cerium dioxide catalyst which is prepared by the preparation method;
The shape of the modified nano cerium oxide catalyst is short rod-shaped nano cerium oxide.
The invention also provides a preparation method of the dimethyl carbonate, and under the action of the modified nano cerium oxide catalyst and the dehydrating agent 2-cyanopyridine, the synthesis reaction of carbon dioxide and methanol is carried out to obtain the dimethyl carbonate.
The surface of the nano cerium dioxide catalyst has a large number of oxygen holes and acid-base sites to promote the adsorption and activation of carbon dioxide, and the nano cerium dioxide catalyst has good catalytic activity and selectivity. In order to improve the yield of the reaction, H 2 O generated in the dehydration reaction is added to be an effective method, a great amount of reports are made on the dehydration agent used for directly synthesizing DMC from CO 2 and methanol, and 2-cyanopyridine is used as a chemical dehydration agent, is a more effective dehydration mode, and can effectively improve the reaction efficiency.
Preferably, the mass ratio of the modified nano cerium oxide catalyst to the methanol is 1:50-100, the CO 2 pressure is 3-5 MPa, and the mass ratio of the methanol to the 2-cyanopyridine is 1:1 to 1.5.
Preferably, the temperature of the synthesis reaction is 120-160 ℃, the reaction time is 1-5 h, and the stirring speed is 400-800 rpm.
Preferably, the dehydrating agent 2-cyanopyridine forms a water absorption product 2-pyridine amide after the synthesis reaction is finished, and the water absorption product 2-pyridine amide is dehydrated to generate 2-cyanopyridine which is used as a liquid phase raw material to be returned to the reaction kettle.
Compared with the prior art, the invention has the beneficial effects that:
The catalyst prepared by the invention uses freeze drying as a drying mode, so that the catalyst has good catalytic activity, and particularly, a remarkable catalytic synthesis effect is obtained in the process of synthesizing the dimethyl carbonate by using methanol and carbon dioxide.
Drawings
FIG. 1 is a TEM image and particle size distribution of a freeze-dried nano-ceria catalyst prepared by the present method.
Detailed Description
The invention is further illustrated by the following examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention includes but is not limited to the following embodiments.
Example 1
9.6G of sodium hydroxide powder was dissolved in 35mL of deionized water, stirred (600 rpm), 0.86g of cerium nitrate was dissolved in 5mL of water, sonicated until cerium nitrate was completely dissolved, added dropwise to sodium hydroxide solution, and stirred for 30min. The suspension was added to 50mL of Teflon liner and aged at 90℃for 12h. Then, the mixture was dispersed by adding absolute ethanol, centrifuged three minutes (8000 rpm), repeated three times, then, dispersed by adding water again, and centrifuged three minutes (8000 rpm), repeated three times. The washed cerium hydroxide was dispersed in 5ml of deionized water, sonicated, and then frozen in a refrigerator overnight. Then freeze-drying is carried out at-70 ℃ for 12 hours. Calcining the dried cerium hydroxide powder at 600 ℃ for 5 hours to obtain the nano cerium oxide catalyst.
The prepared nano cerium oxide catalyst is used for directly synthesizing dimethyl carbonate by using carbon dioxide and methanol, the reaction pressure is 3.5MPa, the reaction time is 3h, the reaction temperature is 140 ℃, the stirring speed is 500rpm, the catalyst dosage is 0.1g, the methanol dosage is 11g, and the dehydrating agent is 8g of 2-cyanopyridine.
Comparative example 1
9.6G of sodium hydroxide powder was dissolved in 35mL of deionized water, stirred (600 rpm), 0.86g of cerium nitrate was dissolved in 5mL of water, sonicated until cerium nitrate was completely dissolved, added dropwise to sodium hydroxide solution, and stirred for 30min. The suspension was added to a 50ml polytetrafluoroethylene liner and aged at 90℃for 12h. Then, the mixture was dispersed by adding absolute ethanol, centrifuged three minutes (8000 rpm), repeated three times, then, dispersed by adding water again, and centrifuged three minutes (8000 rpm), repeated three times. And then dried in vacuo at 70℃for 12h. Calcining the dried cerium hydroxide powder at 600 ℃ for 5 hours to obtain the nano cerium oxide catalyst.
The prepared nano cerium oxide catalyst is used for directly synthesizing dimethyl carbonate by using carbon dioxide and methanol, the reaction pressure is 3.5MPa, the reaction time is 3h, the reaction temperature is 140 ℃, the stirring speed is 500rpm, the catalyst dosage is 0.1g, the methanol dosage is 11g, and the dehydrating agent is 8g of 2-cyanopyridine.
Comparative example 2
9.6G of sodium hydroxide powder was dissolved in 35mL of deionized water, stirred (600 rpm), 0.86g of cerium nitrate was dissolved in 5mL of water, sonicated until cerium nitrate was completely dissolved, added dropwise to sodium hydroxide solution, and stirred for 30min. The suspension was added to 50mL of Teflon liner and aged at 90℃for 12h. Then, the mixture was dispersed by adding absolute ethanol, centrifuged three minutes (8000 rpm), repeated three times, then, dispersed by adding water again, and centrifuged three minutes (8000 rpm), repeated three times. Then air-dried at 70℃for 12h. Calcining the dried cerium hydroxide powder at 600 ℃ for 5 hours to obtain the nano cerium oxide catalyst.
The prepared nano cerium oxide catalyst is used for directly synthesizing dimethyl carbonate by using carbon dioxide and methanol, the reaction pressure is 3.5MPa, the reaction time is 3h, the reaction temperature is 140 ℃, the stirring speed is 500rpm, the catalyst dosage is 0.1g, the methanol dosage is 11g, and the dehydrating agent is 8g of 2-cyanopyridine.
Table 1 shows the methanol conversion and DMC yields of the nano-ceria catalysts prepared under different drying conditions in example 1 and comparative examples 1-2 for synthesizing dimethyl carbonate.
Comparative example 3
The catalyst preparation was as in example 1.
The prepared nano cerium oxide catalyst is used for directly synthesizing dimethyl carbonate by using carbon dioxide and methanol, the reaction pressure is 3.5MPa, the reaction time is 3h, the reaction temperature is 140 ℃, the stirring speed is 500rpm, the catalyst dosage is 0.1g, the methanol dosage is 11g, and the dehydrating agent is 8g of 3-cyanopyridine.
Example 2
The catalyst preparation was as in example 1.
The prepared nano cerium oxide catalyst is used for directly synthesizing dimethyl carbonate by using carbon dioxide and methanol, the reaction pressure is 3.5MPa, the reaction time is 3h, the reaction temperature is 140 ℃, the stirring speed is 500rpm, the catalyst dosage is 0.1g, the methanol dosage is 11g, and the dehydrating agent is 12.5g of 2-cyanopyridine.
Example 3
The catalyst preparation was as in example 1.
The prepared nano cerium oxide catalyst is used for directly synthesizing dimethyl carbonate by using carbon dioxide and methanol, the reaction pressure is 3.5MPa, the reaction time is 4 hours, the reaction temperature is 140 ℃, the stirring speed is 500rpm, the catalyst dosage is 0.1g, the methanol dosage is 11g, and the dehydrating agent is 12.5g of 2-cyanopyridine.
Table 1 comparison of catalytic performances
Qualitative and quantitative analysis of the liquid product using a gas chromatograph (FULI 9790 II) equipped with a hydrogen Flame Ionization Detector (FID) and a SE-54 capillary column (50 m 0.32mm 1 um) showed a significant increase in catalyst activity when freeze-drying was used, DMC yields of 873mmol g -1 cat, selectivity approaching 100%, far exceeding previously reported results.
Claims (6)
1. The preparation method of the dimethyl carbonate is characterized in that under the action of a modified nano cerium oxide catalyst and a dehydrating agent 2-cyanopyridine, carbon dioxide and methanol are subjected to synthesis reaction to obtain the dimethyl carbonate;
the preparation method of the modified nano cerium oxide catalyst comprises the following steps:
(1) Dropwise adding a cerium nitrate solution into a sodium hydroxide solution, and obtaining cerium hydroxide suspension under the stirring condition;
(2) Adding the cerium hydroxide suspension obtained in the step (1) into a reaction kettle for aging, then washing the cerium hydroxide with alcohol and water, dispersing the obtained cerium hydroxide in deionized water, carrying out ultrasonic vibration, freezing overnight, and then carrying out freeze drying;
(3) Calcining the dried cerium hydroxide powder to obtain the nano cerium oxide catalyst;
in the step (2), the freeze drying temperature is-60-80 ℃ and the freeze drying time is 10-14 h;
The shape of the modified nano cerium oxide catalyst is short rod-shaped nano cerium oxide.
2. The method for producing dimethyl carbonate according to claim 1, wherein in the step (1), the stirring speed is 400 to 800rpm, and the stirring time is 20 to 40 minutes;
In the step (2), the aging time is 10-14 h, the times of alcohol washing and water washing are 3-5 times, and the ultrasonic time is 20-40 min.
3. The method for preparing dimethyl carbonate according to claim 1, wherein in the step (3), the calcination temperature is 600-800 ℃, the calcination time is 4-6 hours, and the temperature rising rate is 2-5 ℃/min.
4. The method for preparing dimethyl carbonate according to any one of claims 1 to 3, wherein the mass ratio of the modified nano cerium oxide catalyst to the amount of methanol is 1:50 to 100, the pressure of CO 2 is 3 to 5MPa, and the mass ratio of the amount of methanol to the amount of 2-cyanopyridine is 1:1 to 1.5.
5. A process for preparing dimethyl carbonate according to any one of claims 1 to 3, wherein the temperature of the synthesis reaction is 120 to 160 ℃, the reaction time is 1 to 5 hours, and the stirring speed is 400 to 800rpm.
6. A method for producing dimethyl carbonate according to any one of claims 1 to 3, wherein the dehydrating agent 2-cyanopyridine forms a water-absorbent product 2-picolinamide after the synthesis reaction is completed, and the water-absorbent product 2-picolinamide is dehydrated to form 2-cyanopyridine which is returned to the reaction vessel as a liquid phase raw material.
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| CN111498894A (en) * | 2020-04-28 | 2020-08-07 | 陕西科技大学 | Preparation method of nano cerium dioxide with high catalytic activity |
| CN112823879A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol |
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| CN107774269A (en) * | 2017-09-14 | 2018-03-09 | 天津大学 | Co deposited synthesis copper ceria catalyst, preparation method and application |
| CN112823879A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol |
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